CA2405272A1 - Injection moldable polyamide resin compositions and articles made therefrom - Google Patents

Injection moldable polyamide resin compositions and articles made therefrom Download PDF

Info

Publication number
CA2405272A1
CA2405272A1 CA002405272A CA2405272A CA2405272A1 CA 2405272 A1 CA2405272 A1 CA 2405272A1 CA 002405272 A CA002405272 A CA 002405272A CA 2405272 A CA2405272 A CA 2405272A CA 2405272 A1 CA2405272 A1 CA 2405272A1
Authority
CA
Canada
Prior art keywords
nylon
compositions
polyamide resin
gear
gears
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002405272A
Other languages
French (fr)
Inventor
Masahiro Nozaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2405272A1 publication Critical patent/CA2405272A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16HGEARING
    • F16H55/00Elements with teeth or friction surfaces for conveying motion; Worms, pulleys or sheaves for gearing mechanisms
    • F16H55/02Toothed members; Worms
    • F16H55/06Use of materials; Use of treatments of toothed members or worms to affect their intrinsic material properties

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Gears, Cams (AREA)

Abstract

Polyamide resin compositions are provided that are injection-moldable, and comprising nylon 6 or nylon 6,6 having a RV of from 70-470 (in 90 % formic acid) or nylon 6,12 having a RV of from 2.40 -4.50 (in 98 % sulfuric acid).
The compositions may also include polytetrafluoroethylene powder or high viscouse silicone, and other fillers and additives. These compositions exhibit improved properties, and are particularly suited for gear assemblies.

Description

TITLE OF INVENTION
INJECTION MOLDABLE POLYAMIDE RESIN COMPOSITIONS AND
ARTICLES MADE THEREFROM
BACKGROUND OF THE INVENTION
1. Field of the Invention.
This invention relates to polyamide resin compositions suitable for the to injection molding of articles having high durability. More particularly, this invention relates to such compositions in which the polyamide resin is of a desirable molecular weight and optionally including a variety of additives (including silicone and lubricants), so that articles made therefrom exhibit improved fatigue resistance and low friction properties.
2. Description of Related Art.
Polyamide resin compositions are widely recognized as the materials of choice for any number of molding applications. Significant attention has been directed 2o towards the development of nylons that are stiff, tough, and heat stable.
These properties are desirable from the standpoint of manufacturing articles that can exhibit characteristics required in today's demanding and rigorous end-use applications.
Japanese laid-open application 62-185747 is directed to compositions of polyamide 4,6 (and having a relative viscosity (RV) of greater than 1.5 and preferably 2.5-5.0) in combination with polytetrafluoroethylene powder (less than 15 microns in size), and optionally fillers (0-60 wt%). However, this reference mentions only improved friction performance with 4,6 nylon and does not mention the rationale for selection of the viscosity range (nor the preferred range) nor does it 3o relate properties to the viscosity range.
Japanese laid open patent 9-89081 discloses an injection molding gear for use in general purpose engines, which is formed by inj ection molding a polyamide resin such as polyamide 66 followed by heat treatment, with a relative viscosity measured in a 1.0% concentration solution of 98% sulfuric acid of greater than 3.5.
However, it does not recognize or suggest the problem of adverse effects on a variety of mechanical properties. In particular dimensional accuracy (due to the necessity of heat treatment after molding) can be affected, resulting in a loss of balance of mechanical properties of polyamide moulded gears.
Japanese laid-open application 10-60269 is representative of nylon compositions intended for the manufacture of molded parts. There is disclosed therein high molecular weight polyamides having an intrinsic viscosity greater than 3.0 and in combination with polyolefins. However, its teachings are limited to compression molding applications:
1o Monomer cast nylon 6 is commonly used for gears. However, this is not injection-moldable, limiting its usefulness in a variety of demanding applications.
The monomer cast nylon is available mainly in stock shapes out of which finished products are machined; see the Nylon Plastics Handbook from HANSER, P.542.
This requires two production steps for making gears; namely, cutting of the stock to be a suitable size for the gears and then machining of gear teeth.
Tt is an obj ect of the present invention to provide a polyamide resin composition which is injection moldable, and further which is used to produce articles having improved durability. It is a further object of the invention to provide injection 2o moldable articles that exhibit remarkable fatigue and low friction, with its balance of such properties. One feature of the invention is its suitability for the manufacture of gears (such as automotive steering assist gears, window lifting gears and wiper motor gears) which are capable of withstanding high loads placed on the gear teeth.
This promotes an improvement in the life of such gears. It is an advantage of the present invention that the polyamide resins disclosed herein may include a number of additives which increase fracture toughness, lubricity, and the like. These and other objects, features and advantages of the present invention will become more readily apparent upon having reference to the following description of the invention.

SUMMARY OF THE INVENTION
This invention provides an injection moldable polyamide resin composition comprising nylon 6 or nylon 6,6 having a relative viscosity (RV) from 70 to 470 in 90% formic acid, or nylon 6,12 having a relative viscosity (RV) from about 2.40 to 4.50 in 98% sulfuric acid.
Compositions of the invention may also comprise silicone, in a range of 1-10 to weight percent. Other additives, such as waxy lubricants, aliphatic and/or aromatic acid esters, ether and amides, may also be incorporated into the compositions of the invention, in amounts of 0.05- 5 weight percent. Silicone and waxes in particular have been found to desirably enhance fracture toughness for a specified molecular weight range. Any of the above compositions may also further include olefin 15 elastomers and inorganic or organic fillers, in amounts ranging from 2 to 30 weight percent.
The present compositions are versatile, and may be blended with any of a variety of polyamide resins having a Tg of at least 80 C, and in amounts of from 5- 85 weight 20 percent .
DETAILED DESCRIPTION OF THE INVENTION
The polyamides useful in the present invention comprise nylon 6, nylon 25 6,6 and nylon 6,12. These designations are readily understood by those skilled in the art. For example, representative nylons may be selected from saturated linear nylon homopolymers, such as polycaprolactam (nylon 6) polyhexamethlyene dodeconedicarboxylic acid (nylon6,12) and polyhexemethylene adipamide (nylon 6,6). Useful nylon homopolymers may be produced using adipic acid, azelaic acid, 3o sebacic acid, dodecanedicarboxylic acid, isophtharic acid or terephthalic acid, and in conjunction with hexamethylenediamine, 2-methyl-pentamethylenediamine, octamethylendiamine, nonamethylendiamine, 2-methyl-octamethylenediamine, trimethylhexamethylenediamine, bis-(4-aminocyclohexyl)-methane or 2,2-bis(4'-aminocyclohexyl)-propane. Polyamides with a Tg of at least 80 C typically contain at least 20 mol% of aromatic monomer. These may be manufactured using a variety of techniques also readily known and appreciated among those skilled in the art. For example polymerization in an autoclave one step or continuous polymerization by applying suitable pressure and temperature is taught in U.S.Patent No.5,378,800 incorporated by reference herein. An alternative process includes preparing a prepolyrner and subjecting the prepolymer to solid-phase polymerization or melt-mixing in an extruder to increase the degree of polymerization. Further, the above polymerized polymer is further polymerized by solid-phase polymerization in order to increase molecular weight.
The nylons described above and in the RV ranges set forth herein may also be blended with other materials having a high glass transition temperature. The selection of the appropriate blend is a function of the end use of the polymeric material.
The aforementioned polyamides are preferable for a number of applications requiring high durability, such as gears in which the gear teeth are under exceptional loads. One such area of interest is automotive steering assist gears, which are subject to loading environments that often cause gear teeth to chip or fracture.
Specifically, these polyamides in the RV ranges specified impart injection-moldability to the compositions, thereby significantly improving fracture toughness as compared to standard grades of polyamides. This higher fracture toughness is a critical factor for longer gear life and provides high fatigue resistance.
It should be noted that while some gears contemplated herein are preferentially made through the injection molding process and include gear teeth formed thereon, other gears of interest are first injection molded and next undergo machining operations to form the gear teeth. Both concepts are considered within the purview of the invention disclosed herein.
There are two factors essential to the promotion of long gear life - fatigue resistance and low friction. The polyamides identified as above are well suited for parts which must exhibit these properties. The high molecular weight of the polymer is found to provide high fracture toughness, which in turn promotes high fatigue resistance. This property is very important for longer gear life because the gear teeth must resist repeated impact from other gears and gear teeth during power transmission. Broken gears are often associated with fatigue.

Low friction - the other factor - provides less heating of the gear teeth by friction between gears. Polymer when heated up exhibits a lower strength and modulus (eg it is easy to deform).
Another benefit associated with the compositions of the invention is that the compositions do not require heat treatment after injection molding, and the dimensional stability is observed.
Any of a number of additives may be incorporated with the polyamides l0 disclosed herein to enhance low friction properties between the gears.
These include without limitation polytetrafluoroethylene (PTFE) and silicone, and preferably silicone. Further, waxy lubricants such as aliphatic and/or aromatic esters, ethers and amides, desirably enhance fracture toughness for a specified molecular weight range.
15 In addition, fillers of inorganic or organic have been identified as improving creep resistance; these include inorganic fillers such as wollastenite, kaolin, talc, mica, almina, silica, magnesium oxide, calcium silicate, magnesium silicate, metal whisker, potassium titanate whisker and the like organic fillers such as carbon fiber, aramid fiber (for example KEVLAR~ brand fiber available from EI
2o DuPont de Nemours and Company), etc. These fillers are added during compounding or injection molding process with the polyamide.
A number of olefin elastomers have been identified as useful to incorporate into the polyamide compositions of the invention. For example, an elastomer of ethylene- -olefin, ethylene-propylene-dime, ethylene-unsaturated 25 carboxylic acid, ethylene-unsaturated carboxylic acid ester, ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid ester, -olefin-unsaturated carboxylic acid, -olefin unsaturated carboxylic acid ester, -olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester, ethylene- -olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester; and modified materials of the above-mentioned 3o elastomers in order to graft to polyamides. The modification is done by addition of organic acids such as malefic anhydride, fumaric anhydride, or etc.
The invention will be better understood upon having reference to the following examples of the invention.

EXAMPLES
Test Method Testing for energy for breakage was conducted using molded specimens having the following dimensions: l2mrn high x 125 mm in length x 3.2 mm in thickness. The mold specimen has a notch with identical in both shape and size to that set forth in the ASTM D256 test at the center of test specimen. The testing proceeded in the manner that the specimen was bent from the opposite side of the notch. The test speed of to bending was lOmm/minute and the span for the bending test was 50 mm. Energy for breakage was calculated in the following manner: calculate area of stress-strain curvature up to break and then divide by initial volume in-between the span.
Higher fracture toughness was estimated by higher energy for breakage.
Testing for friction coefficient was conducted using tensile bars based on ASTM
D638, and measured at lHz, 32.5mm ampritude under 2.Okgf load.
Molding conditions for nylon 6,6 and nylon 6,12 included a mold temperature of 65 C and a melt temperature of 300 C.
RV is expressed in relation to formic acid or sufuric acid.
2o For example, for nylon 6,6 the RV range in 90% formic acid was determined by dissolving a 2.2g of polyamide in 20 mI of 90% formic acid. For nylon 6,12 the RV
range in 98% sulfuric acid was determined by dissolving a 0.25g of polyamide in 25 ml of 98% sulfuric acid.
Test Compositions and their Properties The details and findings of the experimental work can be found in the following table Example 1-3 and Comparative Example 1.
Nylon66 compositions containing about 0.4% of inorganic heat stabilizer (HS) and with various relative viscosities (RV) were prepared as in table 1.
Energy for breakage and friction coefficient were measured.

Example 4-5 and Comparative Example 2.
Nylon612 composition with various relative viscosities (RV) were prepared as in table 2. Energy for breakage and friction coefficient were measured.
Example 6-8 and Comparative Example 3.
Nylon66 compositions containing about 0.4% of inorganic heat stabilizer (HS) and with various RV were prepared as in table 3. Example 6-7 contains BY27-005 to (nylon66:Silicone gam 50:50) and Example 8 contains waxy lubricant, ethylene glycol di-stearate. Energy for breakage and friction coefficient were measured.
Example 9-12 and Comparative Example 4.
Nylon66 compositions containing about 0.4% of inorganic heat stabilizer (HS) and with various RV was prepared around 70 as on the table 4. Example 9-12 contain various type of waxy lubricants, such as N-Stearyl ercamide and poly ethylene glycol 2-ethyl hexoate. Energy for breakage and friction coefficient were measured.
Overall, it was found that certain ranges of RV values provided higher 2o energy for breakage, which expects to improve fatigue and creep resistance (ex. 1-S).
The addition of silicone and wax into the subjective RV nylon 66 also provided higher energy for break than that of the subjective RV (ex. 6-12).
Table 1 Example Example Example Compara.

Nylon66 + HS 100.00 100.00 100.00 100.00 Energy for breakagekg.cmlcm32.4 6.6 12.0 1.6 Friction coefficient 0.29 0.27 Table 2 Example 4 Example Compara.
Nylon 612 100.00 100.00 100.00 RV 2.72 3.12 2.28 Energy for breakage kg.cm/cm 4.8 9.1 1.9 Friction coefficient 0.30 0.30 Table 3 Example Example Example Compara.
Nylon66 + HS 95.00 90.00 99.00 100.00 BY27-005 (Nylon66/ Silicone 5.00 10.00 gam 50!50) 1.00 Ethyelene glycol di-srearate Energy for breakage kg.cm/cm 3.7 4.5 3.3 2.5 Friction coefficient ~ 0.22 0.20 0.28 Table 4 Exam Exa !e Exam Com ara.
!e 2 !e 3 1 N 1on66+ HS 100.00 100.00 100.00 100.00 Rv 73 162 250 48 Ener y for breaka 2.4 6.6 12.0 1.6 a k .cm/cm3 Friction coefficient 0.29 0.27

Claims (5)

What is claimed is:
1. An injection moldable polyamide resin composition comprising nylon 6 or nylon 6,6 having a relative viscosity (RV) from 70 to 470 in 90% formic acid, or nylon 6,12 having a relative viscosity (RV) from 2.40 to 4.50 in 98% sulfuric acid.
2. The composition of Claim 1 further comprising silicone, in an amount of 1-weight percent.
3. The composition of Claim 1 further comprising an additive selected from the group consisting of waxy lubricant, aliphatic and/or aromatic ester, ether and amides, in an amount of 0.05- 5 weight percent.
4. A gear manufactured from any of the compositions of Claims 1, 2 or 3.
5. A method for the manufacture of a gear from the compositions of Claims 1, 2 or 3 by first injection molding said gear and next machining said gear to form the gear teeth.
CA002405272A 2000-05-17 2001-05-17 Injection moldable polyamide resin compositions and articles made therefrom Abandoned CA2405272A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US20480400P 2000-05-17 2000-05-17
US60/204,804 2000-05-17
PCT/US2001/016008 WO2001088038A2 (en) 2000-05-17 2001-05-17 Injection moldable polyamide resin compositions and articles made therefrom

Publications (1)

Publication Number Publication Date
CA2405272A1 true CA2405272A1 (en) 2001-11-22

Family

ID=22759500

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002405272A Abandoned CA2405272A1 (en) 2000-05-17 2001-05-17 Injection moldable polyamide resin compositions and articles made therefrom

Country Status (4)

Country Link
US (1) US20020019471A1 (en)
EP (1) EP1282665A2 (en)
CA (1) CA2405272A1 (en)
WO (1) WO2001088038A2 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006152999A (en) * 2004-10-29 2006-06-15 Honda Motor Co Ltd Resin cam gear
KR101370832B1 (en) * 2012-09-11 2014-03-10 주식회사 만도 Reduction gear for electric power steering and method for manufacturing thereof
TWI794146B (en) * 2015-12-01 2023-03-01 美商阿散德性能材料營運公司 High molecular weight polyamides and copolyamides with uniform rv and low gel content

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3707522A (en) * 1968-06-27 1972-12-26 Fiber Industries Inc Polyamide composition and process
JP3144927B2 (en) * 1992-12-02 2001-03-12 旭化成株式会社 High strength polyamide fiber and method for producing the same
JPH0989081A (en) * 1995-09-28 1997-03-31 Fuji Heavy Ind Ltd Injection molding gear for general purpose engine and manufacture thereof
US5872175A (en) * 1997-07-08 1999-02-16 Hyundai Mortor Company Polyamide resin composition
US6011134A (en) * 1998-01-30 2000-01-04 E. I. Du Pont De Nemours And Company Method for manufacturing poly(hexamethylene adipamide) from monomethyladipate and hexamethylenediamine

Also Published As

Publication number Publication date
EP1282665A2 (en) 2003-02-12
US20020019471A1 (en) 2002-02-14
WO2001088038A3 (en) 2002-05-02
WO2001088038A2 (en) 2001-11-22

Similar Documents

Publication Publication Date Title
JP5916762B2 (en) Melt blended thermoplastic composition
US4446304A (en) Highly stable nylon 4,6 objects
KR101644200B1 (en) Heat Resistant Molded or Extruded Thermoplastic Articles
JP5640975B2 (en) Polyamide resin
EP1826242B1 (en) Polyamide resin composition containing glass fiber
CA2425238C (en) Polyamide resin composition
JP2006152256A (en) Polyamide resin composition and molding comprising the same
JP2003055549A (en) Polyamide composition
CA2014243A1 (en) Polyamide resin composition
US5750639A (en) Polyamide resin composition and molding thereof
EP0741762B1 (en) Polyamide resin composition and molding thereof
JP3462849B2 (en) Polyamide resin, polyamide resin molded product, and method for producing the molded product
JP2006176597A (en) Polyamide resin composition
US20020019471A1 (en) Injection moldable polyamide resin compositions and articles made therefrom
US20040010094A1 (en) Injection moldable polyamide resin compositions containing poly carbo-di-imides and articles made therefrom
JP2004107525A (en) Polyamide composition
KR101740687B1 (en) Polyamide based polymer compositions having good flowability and polyamide based composite material using the same
CN106893319B (en) Polyamide resin composition having high heat resistance and oxidation resistance
KR101795675B1 (en) Polyamide based polymer compositions comprising cyclic compound and polyamide based composite material using the same
JP4150136B2 (en) Polyamide resin composition
CN114573945A (en) Thermally stable polyoxymethylene compositions
JP2000191905A (en) Polyamide resin composition
JPH0948914A (en) Molded gear
KR102292133B1 (en) Polyamide resin composition and article comprising the same
JP2952930B2 (en) Polyarylene sulfide resin composition

Legal Events

Date Code Title Description
EEER Examination request
FZDE Dead